Production of dental prosthesis

ABSTRACT

An improved composition for use in the production of dental prostheses, comprising 85-60 parts of a polymer of methacrylic acid and 40-15 parts of an acrylic acid ester/methyl methacrylate or methacrylic acid ester/methyl methacrylate copolymer, where the ester content in the copolymer, the molecular weight of the polymer and copolymer, and the particle size of the polymer and copolymer are required to be within specified ranges to obtain a rapid start of processing and a processing time of at least one hour when the composition is used.

United States Patent 1 1 Logemann et al.

[ 1 PRODUCTION OF DENTAL PROSTHESIS [75] Inventors: Heino Logemann; Paul-Gunther I Bruckmann, both of Leverkusen,

Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany 221 Filed: Nov. 15,1971 [21] App1.No.: 198,944

Related US. Application Data [62] Division of Ser. No. 844,158, July 23, 1969, Pat. No.

[30] Foreign Application Priority Data July 23, 1968 Germany P 17 69 840.7 July 23, 1968 Germany P 17 69 839.4

[52] US. Cl. 260/885, 260/31.8 M, 260/901 264/16 [51] Int. Cl. C08! 15/18 [58] Field of Search 260/885, 901- 5 1 References Cited FOREIGN PATENTS OR APPLICATIONS 671,045 4/1952 Great Britain 260/901 1 3,758,642 1 Sept. 11, 1973 709,983 6/1954 Great Britain 260/901 760,344 10/1956 Great Britain 260/901 Primary Ex ami ner Murray Tillman Assistant Examiner .l. Ziegler Attorney-Jacobs & Jacobs 57 ABSTRACT An improved composition for use in the production of dental prostheses, comprising 85-60 parts of a polymer of methacrylic acid and 40-15 parts of an acrylic acid ester/methyl methacrylate or methacrylic acid ester/- tion is used.

23 Claims, No Drawings 1 PRODUCTION OF DENTAL PROSTHESIS This application is a division of our copending application Ser. No. 844,158, filed July 23, 1969, now US. Pat. No. 3,649,608, issued Mar. 14, 1972.

Synthetic materials for the production of dental prostheses are now predominantly preparedaccording to the powder-liquid process (German Patent S'pecification No. 737,058, Kulzer). A fine-particle polymer powder, usually a bead polymer, which generally consists of polymethacrylic acid methyl ester is formed into a paste in a cruciblewith a liquid predominantly consisting of monomeric methacrylic acid methyl ester in a ratio of 2 3 parts of powder to 1 part of liquid. The

hollow mould of plaster present in a two-partdental flask is usually isolated with an aqueous sodium alginate solution. The paste of powder and monomeric liquid is then introduced, the dental flask is closed by compression and the contents are completely polymeris frequently the custom in practice to dose both ingredients by eye according to the absorption power of the powder for the liquid. it has hitherto not been possible to produce a powder which could be automatically strewnin in such a high proportion, which could be I processed within three to four minutes or less while, on

the other hand,.having a workability. of at least one hour, and which also yielded a satisfactory consistency of the paste.

ised at elevated temperature, usually on a boiling water bath, with the aid of benzoyl peroxide added to the powder. The good physical properties of the polymethacrylic acid methyl ester and the easy handling have caused the process to develop into'a standard technique of dental prosthetics. Some advances made in the course of time have further improved the technique. A substantial consideration is the processing property. Initially the powder, consisted of a pure polymethacrylic acid methyl ester. A finely divided powder of this compound swells in monomeric methacrylic acid methyl ester only after about 18 20 minutes to such an extent that a plastic paste is formed which is readily workable. After a further 15 minutes, the paste has already become so tight and scabby that it is no longer usable. Even within the processing range of 15 minutes, the plasticity of the mass changes constantly; it is therefore not very easy to catch the desired moment for pre- 7 cision work, and in cases where embedding is difficult there is not sufficient time, the more so as the available periods of time become even shorter at anelevated room temperature. The initial attempt'to improve matters by the addition of plasticisers, such as e.g. phthalic acid dibutyl ester, understandably, proved to be not very successful. The next step for developing an improved processing technique logically consisted in using copolymers, instead of a methacrylic acid methyl ester homopolymer; the improvements thus achieved in respect of processing range and also in the consistency of the paste were already remarkable.,,The finer the particles of the polymer powder, the faster the paste became workable, but the processing range decreases. Mixtures of a polymer powder of predominantly pure polymethacrylic acid methyl ester with a copolymer of methacrylic acid methyl ester and anothervinyl or divinyl compound, primarily an acrylic 'acid ester ,or-a

methacrylic acid ester of a higher alcohol, have permit-.

ted ofa processing range of one hour or more (German Patent Specification No.940,493). There resulted not only a substantial improvement of the flow, butthe consistency of the paste changed much more slowly within the period of. time of one hour; consequently, the man skilled in the art can more easilyselect the consistency adequate to the. work concerned 'andhe has sufficient time to carry out several, even complicated tasks in succession with one pasting operation} The volume of the monomericcomponent decreases during polymerisation. The addition of a polymer powder as filler reduces the shrinkage. Consequently, the

It has now been found that an optimum of all the processing properties, i.e. an automatic strewability of 73 75 parts by weight of powder per 27 25 parts by weight of liquid, a rapid start of processing of 2 4 'minutes, a range of processing of one hour, a paste which has a good flow and the consistency of which changes only very slowly, can be achieved by using as v the powdery component a mixture prepared in a ratio of 85 60, preferably 80 70 to,

' Partsof l. a preferably bead-shaped polymer of methacrylic acid methyl ester containing from O to 2 percent of an additional comonomer and having a K- value'of or 75 +120, preferably 80 100, and a sieve analysis of at least 98 percent particles which are .smallerthan 125 p. and more than .50 percent of particles which are larger than 63 n; Per 15 40, preferably 20 30 parts, of 2. one or more preferably bead-shaped copolymers which are synthetised from 15 30, preferably 20 25, parts by weight of 'one or more acrylic acid esters the balance being methacrylicacid methyl ester and 0 to 5 percent of a further comonomer, and which have a 1(- value of between 76 and 95 and a sieve analysis of at least. 1-5 percent, preferably not more than 80 percent, of particles above 100 n, or

2A. one or more bead-shaped copolymers which are synthetised from 18 30 parts by weight, preferably 20 -.,25 parts by weight, of one or more methacrylic acid esters with seven to 14 carbon atoms in the alcohol residue (possibly'in mixture with minor proportions of other (meth)acrylic acid esters) and the balance being methacrylic acid methyl ester with 0 to 5 percent by weight [of a further comonomer, and which have a K- I value between 76 and 80 and a sieve analysis of at least 10 percent, preferably more than 25 percent, of particles above 80 .4., or a'K-value between 80 and 90 and a sieve analysis of at least 25 percent of particles above (meth)acrylic acid esters) and the balance being methacrylic acid methyl esters with 0 to 5 percent by weight ofa further comonomer, and which have K-values between 76 and 95 and a sieve analysis with at least 15 perceriL-preferably at least 25 percent, of particles above80 p.. Y

The K-value is a measure of the viscometric molecular weight. The viscosity of a 0.5 percent solution of the polymer in chlorobenzene is measured at 25C, and the result is expressed in the form of the K-value which is virtually independent of the concentration, according to H. Fikentscher, Cellulosechemie 12 (1932), 60.

The desired simultaneous peak in all the processing properties is thus achieved by determining in the components of the mixture within certain limits the chemical composition as well as the molecular weight and also the particle size. The copolymer is usually coarser than the homopolymer.

Suitable polymer powders for the homopolymer of methacrylic acid methyl ester as well as for the copolymer are primarily bead polymers, although admixtures of e.g. splinter polymers are not excluded. In the Examples the sieve analyses have been carried out with test sieves according to DIN standard. The polymers produced according to conventional processes for bead polymerisation give a distribution curve which can be illustrated in a logarithmic granulation net by a straight line. Any deviations which may be caused by special operations are to be related thereto.

For use in forming the copolymers, the acrylic acid esters preferably comprise the esters of acrylicacid with simple aliphatic alcohols containing one to 15 carbon atoms, especially one to 8 carbon atoms, and the methacrylic acid esters preferably comprise esters of On the other hand, polyhydric alcohols would essentially change the picture, even if admixed in very small amounts.

It has been known for a long time to use mixtures of different polymers for the powder-liquid process. For.

example, U.S. Pat. specification No. 2,569,767, Knock et aL, column 5, line seq. remarks on the use, in particular, of dichlorostyrene as monomeric liquid that polymers with different solubilities in the monomer can be used in order to influence the consistency of the physical form of the mixture prepared: For example, a mixture of a polymer of low solubility in the monomer with a polymer of high solubility often yields the desired consistency when a single polymer of the same solubility characteristics is ineffective. Approximately the same result can sometimes also be achieved with a mixture of components of one and the same polymer of different particle sizes. And further on in column 1 1: Excellent results are achieved when different low molecular polymers are mixed with their higher molecular polymers to give a mixture of the desired dissolving speed.

An addition of 3 or 15 percent polymethacrylic acid butyl ester is contained, for example, in U.S. Pat. specification No. 2,468,094, Marks, Example 5, and in U.S. Pat. specification No. 2,326,531, Gates; and similarly also in US. Pat. Specification No. 2,321,048, Schildknecht.

According to U.S. Pat. specification No. 2,466,040, S. Myerson, special colour effects are achieved when a coloured polymer powder is mixed with an uncoloured powder, e.g. in a ratio of l 1, the coloured powder preferably having finer particles. In general, however, it is still common use to add the colour pigments as such to the powder mixture or subsequently to cause them to adhere to the surface of the powder particles, that is to say not to use specially coloured polymer components.

In German Patent Specification No. 940,493 a beadshaped homopolymer of methacrylic acid methylester is mixed, as already mentioned above, with afinely divided copolymer of methacrylic acid methyl ester and acrylic acid esters or butadiene or methacrylic acid esters of alcohols with more than 4 carbon atoms..-The copolymer is characterised by the property of swelling with monomeric methacrylic acid methyl ester within a shorter time than the homopolymer, due to the .degree of dispersion and the chemical composition. In the usual range of particle size from 20 y. to about 200 u.

were to be more finely divided than the homopolymer.

It is true, that Example 1 mentions a copolymer of 80 parts by weight methacrylic acid methyl ester and 20 parts by weight methacrylic acid dodecyl ester of an av-.

erage bead diameter of 0.1 mm, which ismixed with a homopolymer of 0.07 mm. However, this is a typing error which was overlooked. The text of the application which was subsequently restricted states: -dodecyl ester with a K-value of and an average bead diameter of such a size that this copolymer alone with the monomer forms virtually at once a .kneadable mass which and the English text (British Patent Specification No. 760,344) states 0.02 mm.

The content of German Patent Specification No. 940,493 appears also in U.S. Pat. specification No. 2,947,716 German published specification No. 1,251,948 published 10.12.1967), restricted.to'a copolymer with 7.5 4 40 percent by weight acrylic, acid ethyl ester in an admixture of 7.5 to 48 percent by weight (in U.S.' Pat. specification No. 2,947,716 also acrylic acid methoxy ethyl ester and acrylic acid butoxy ethyl ester). However, no instructions are given for the selection of the particle sizes and molecular weights; In column 5, line 37 of the U.S. Patent Specification it is stated that other acrylates, .e.g.. butyl acrylate, are .inoperative? with regard to the inventiomso that the application is limited to methoxy ethyl acrylate andpreferably ethyl acrylate. Very important is, furthermore, the statement made, in the Claim of [German published specification No. 1,251,948 which corresponds to the hitherto state of the art, that the quantity of monomeric liquid should amount to 50 to 30 partsby weight per 50 to 70 parts by weightof powder. In contrast thereto, the process of the present invention :achieves an automatic addition in a proportion of 27v to 25.parts of'monomeric liquid to 73 to 75yparts of powder, i.e.- very nearly the ratio 1 3.

It is furtherrknown that the addition of -a polymer of times smaller; that is also described in Swiss Patent Specification No. 279,640 in thename of Lonza (Ger.-.

man patent application L 3646 Austrian Patent No. 176,360 British Patent Specification'No. 709,983) for cold-setting: dentalmateriaLI-Iowever, since nowadays dental materials normally have an average particle,

achieve the desired properties of the powder mixture when preparing the paste. Only the combination of the two components, the homopolymer and the copolymer, each with the claimed properties, offers the possibility of achieving all the desired properties of the paste ,simultaneously. From German Patent Specification No. 940,493 there is known the effect, which was surprising at the time, that processing times of over 1 hour can be achieved by admixing copolymers of acrylic acid esters or of methacrylic acid esters containing four to car,- bon atoms with methacrylic acid methyl ester. Copolymers of methacrylic acid methyl ester with acrylic acid esters or methacrylic acid esters of alcohols containing four to 15 carbon atoms, which are composed according to the said patent specification swell by themselves I with the monomeric liquid very fast within a few section. Furthermore, too coarse a polymer would give macroscopically recognisable grain edges, especially in the coloured state, and poorer physical properties in the finished prothesis. When the molecular weight of the copolymer as well as of the homopolymer are sufficiently high for the paste tobe workable within two to four minutes, an automatic addition ratio of three parts onds to yield a paste which, if it is at all usuable, be-

comes completely useless within a few minutes. If in the present invention only one factor in the properties of the components is modified, seriousdisturbancesinthe property image of the mixture with themonomeric liquid arise at once and all the demands can no longer be met simultaneously. If the molecular weight of the copolymer as well as of the homopolymer. is too low, stirring of the powder mixture with monomeric methacrylic acid ester yields a paste which has awide range of processing, possibly of two hours or more, but the mixture achieves a satisfactory cohesion only after more than 6 minutes. When the powder is added to the monomeric liquid, a moist, loose, sugary mass is'initially obtained in these cases which becomes cohesive only after mixing for a prolonged time, which is slow to become detached from the crucible wall and loses its tackiness even later. When the molecular weightof both components, especially of the copolymer, is increased, the paste attains a consistency suitable for processing within a much shorter time. Spatulating can be starting immediately after mixing the powder with the liquid since, due to the higher viscosity of the dissolved and swollen components, the mass becomes almost immediately cohesive. On the, other hand, thetackiness caused by the swelling and dissolving disappears much more rapidly so that the mass soon becomes detached from the crucible wall and rapidly matures to form a homogeneous smooth and velvety supplepaste of a good compression consistency. if the molecular of powder for every part of monomeric liquid and the desired workability of one hour are achieved only if the conditions stated in the claim for the sieve analysis are met for the copolymer as well as for the homopolymer.

When the molecular weight is further increased, the

limitsare determined by the fact that an increasing molecular weight of the copolymer causes the spatulated mass to become rough and too tight sooner than does that of the homopolymer, that the mixed paste acquires an increasingly elastic, loose or cotton woolslike feel after a short time, and that the time available for processingfalls below the value of one hour. Accordingly, limits are defined by the content ofacrylic acid ester or methacrylicacid esters of higher alcohols in the co-.

polymer; if the content istoo low, the swelling power becomes too low, if it is toohigh, the swelling power 1 becomes toostrong. If, therefore, any of the requirements according to the present invention for the homopolymer and the copolymer are not carefully followed, the properties of the material immediately become more unfavourable in one or several respects. An optimum'can only be achieved by the combined effect of allthe properties of the powder mixture in strict accordance with the invention. H

Even within thedeflned range, smaller gradations are still recognisable. For example, a coarser particle size will be chosen for the copolymer as the proportion of acrylicacid ester or methacrylic acid ester of high alcohols in the copolymer and the molecular weight increase. Consequently, a certain range of validity exists for the states parameters, within which they remain applicable. Howevenonly their sum total gives the possibility of simultaneously combining all the properties mentionedabove in the product.

Finally, a compensation of the properties can also be achieved in some cases by using, within the stated limits, different copolymers of the claimed type at the same time. Furthermore, an addition of plasticisers, such as e.g; dibutyl phthalate, in quantities of up to about 5 percent, referred to the polymer, are not excluded in principle, although this will generally be omitted. Further additives, such as dyestuffs, lubricants, anti-ageing agents etc., are used in known manneraccordingto the state of the art.

Asmall proportion of other comonomers, e.g. sty- 1 Y rene or vinyl acetate, of not more than 2 percent in the weights of both components lie withinthe stipulated order to achieve a supple, velvety paste the structure of a which is not noticeable during kneading, the lower limits being determined by the demand for automatic addihomopolymer and not more than 5 percentin the coa polymer is admissible.

. 'An-appreciable advantage is achieved in many cases when the homogeneous polymer ofpredominantly pure methacrylic acid methyl ester with K-values of 75 120, preferably 100, anda sieve analysis of at least 98 percentof particles below uand at least 50 percent of particles above 63 p. isreplaced in the process described above with a mixture of such a polymer with a similar. polymer where the diameter is 2 to 5 times smaller. The advantages thus attainable consist in that in these cases coarser homopolymers of methacrylic acid methyl ester can also be used, i.e.' those the sieve analysis of which contains at least 99 percent of partimedlately, rough becomes outside. stringy,

I somewhat moist, than good andsmooth Not inhomo 4'40" geneous,

soft and somewhat moist, not

very

tight. Good 2'45" 0.4 do Initially 4 0.6 Hardly wet.

cles below 150 y. and at least 50 percent of particles 03 5 above 63 .1.. It is common procedure to mix polymers E e gil of the same type but of different granulation, in order mg 53338 3 8 3 3 to produce mixtures which can be thermoplastically Egg processed, for example, pastes of polyvinyl chloride 5 a-EEglE-i :3 f 5;, powder and plasticisers, with the lowest possible prom E3 portion of liquid. Austrian Patent Specification No. Z 171,172 of May 23, 1949 in the name of Lonza, Swiss 5 a a 5 g s priority June 14, 1948 (cf. also Swiss Patent Specifica- E i g g tion No. 279,640 in the name of Lonza for cold-setting 10 g E 2 ,3338 5 dental masses) proposes to add a polymer the average 3 I I m particle size of which is at least six times smaller. A E I "335 polymer of methacrylic acid methyl ester with the Z 2 :8 :8 :8 s a 5M9 'N a N N range of particle s1ze from about 1 20 y. is not easily 5 r produced on an industrial scale, and it would impart a g i dusty character tothe material. Optimumeffects are a {g E; E; o 'g'lgfieg'g already achieved when 5 50 percent by weight of the "g EE 31%; homopolymer of methacrylic acid methyl ester are re- 5 Q E o i placed with a similar homopolymer the average diame- 5 a ter of which is 2 5 times smaller. Not only can the E 21 B 33-:158u5 5 1: powder be strewn mto a smaller amount of l1qu1d, the 2'3 :3 a z spatulated paste also becomes more rapidly homogeq q neous, it is noticeably more supple and smoother, al- 32335; though normally workable for a somewhat shorter pe- '5 riod of time, but this is irrelevant when without this 25 3E e measure the range of processing substantially exceeds T3 T 3 2:; the period of time of one hour which is hardly ever fully utilized. If, on the other hand, the homopolymer of g, methacrylic acid methyl ester is finer throughout, the F2 5. 2 g 3 l a g mixture with the copolymer proves to be more difficult q? 8 to strew in, as described above. f 21% g 3 g s ia a? s 2 EXAMPLE I E g g Seventy-five Parts by weight and 72.5 parts by 35 2 m m weight, respectively, of a bead polymer of pure meth- E E '33 acrylic acid methyl ester of K-value 91.8 and the fol- :935; lowing sieve analysis: 32 ig g E 2 per l25 100 80 63 40 p. through 40 p. Q 5 0 '14 3o 20 20 16 percent 40 g 3 m g are mixed with 0.25 parts by weight benzoyl peroxide g 3 -55 1% E553? and with 25 and 27.5 parts by weight,'respectively, of g 5 5: E3 a bead polymer obtained by copolymerisation of methi I acrylic acid methyl ester and acrylic acid ethyl ester. E .5- 15 Each time, 12 g of the mixture are strewn into 4 g Egg g? 4.25 cc of monomeric methacrylic acid methyl ester, z the weight of the non-absorbed powder is determined, ig 2 a, g. this is returned and the processing properties are deter- .3% =5. mined. s c a N N RE; EXAMPLE 1 v M g g 2 a N g It can be seen from the Table how the content of g l acrylic acid ethyl ester in the copolymer, its viscomet- E 8 g 2 I w ric molecular weight, given in the form of the K-value, a v Q m q and the granular size influence the processing properf ties of the mixture of the two components with a mono- 43 a N 8 o meric methacrylic acid methyl ester. E g n The mixtures l, 2, 6-and 9 are within the claimed 5 .g E E g g; range in respect of' the content of acrylic acid ethyl L: l i ester in the copolymer (20 percent) and of the molecular weight (K-value of the copolymer 80.3, 81.8, 85.0 i i l 5 and 91.5), but the sieve analyses indicate that the parti- '2. '1 cles of the copolymer are too fine. Consequently, the m m' powder cannot be automatically strewn into the mono- M I merie methacrylic acid methyl ester; 12 g leave a resig a a a due of more than l g. Especially if the molecular weight E E a; is very low (experiment 3, K-value 82.1) and the particles of the copolymer are coarse, the material can com-.

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The mixtures 1, 2 and 3 contain a very coarse methacrylic acid methyl ester homopolymer with a substantial proportion of particles above 125 p. and a comparae tively low molecular weight, K values below 80. The mixture can easily be strewn in, especially at a low K- value, but the paste sets only gradually. When the mass has become detached from the crucible wall and canbe kneaded, it is initially inhomogeneous and tacky. .The tackiness persists for a comparatively long time; on the other hand, the paste remains workable for more than one hour. The coarse grain of the homopolymer-is noticeable during kneading.

The mixtures 4, 5 and 6 are examples ofa homopoly met the grain of which is too fine; the molecular weight, the K-values increase: 78.7, 83.2 and 87.7. The powder mixture cannot be added in the desired proportion; the mass is somewhat viscous and tight when spatulated, but yields a smooth paste which'is soon workable and remains usable for a satisfactory period of time. The mixture 7 exhibits too coarse a grain of the homopolymer and a higher molecular weight than in the mixtures l, 2 and 3. The powder can'still be strewn in, but the spatulated mass is rough and viscous, the paste is inhomogeneous at first. The mixtures 8, 9 and 10 correspond to the desired properties. The addition properties are good, spatulating is easy; a smooth paste is formed within a short period of, time and remains workable forat least 1 hour. The mixture 1 l is a homopolymer with a very high molecular weight, the grain is somewhat too coarse; in the rough and somewhat dry 40 character of the paste and the short duration of workability, the high molecular weight becomes already recognisable as the limit. The mixtures 12 and 13 also relate to homopolymers with a similarly high molecular weight but a finer grain, the proportion of fine particles being even higher in 12 than in 13. The addition property is poor, the paste becomes more or less rough and the period of time for which it remains usable is reduced. v

EXAMPLE 3 Seventy-five Parts by weight and 72.5 parts by weight, respectively, of pure methacrylic acid methyl ester with a K-value of 91.8 and the following sieve analysis: per 125 100 80 63 40 t through 40 p.

0 14 30 20 2O 16 percent are mixed with 0.25 parts by weightbenzoyl peroxide 50 and with 25 and 27.5 parts by weight, respectively-,of a bead polymer obtained by copolymerisation of methacrylic acid methyl ester with acrylic acid butyl ester. Each time, 12 g of the mixture are strewn into 4 g 4.25 cc of monomeric methacrylic acid methyl ester, 65 the weight of the non-absorbed powder is determined,

. this is returned, the mass is immediately spatulated, and

the processing properties are determined.

RE: EXAMPLE 3 The mixture 14 is an example of a mixture of two different acrylic acid esters.

if the processing properties at the mixture ratio of 72.5 parts by. weight of copolymer to 72.5 parts by weight of homopolymer are compared with those at the mixture ratio of 25 75, the powder of the former exhibits slightly poorer strewing properties throughout;

on the other hand, the paste is usually somewhat tighter during spatulating but it is equally smooth and equally proportion. The paste with the coarser copolymer is somewhat less advantageous during spatulating, it is initially moist, sugary; both mixtures set somewhat. slowly because the content of acrylic acid butyl ester is near the lower limit; when the paste can be kneaded, it is at first slightly moist and usually somewhat inhomogeneous, but it remains workable for ove'r'one' hour. The two mixtures approximately characterise the lower limit of the chosen range in respect of the conworkable if the other conditions are within the defined limits.

With a predetermined homopolymer and a copolymer the essential properties of which aredetermined by the patent-claim, it is thus still possible to achieve a certain improvement within these limits in one series with a modified mixture ratio between the homopolymer and the copolymer.

EXAMPLE 4 72.5 Parts by weight of a bead polymer of pure methacrylic acid methyl ester with the K-values and sieve Processing properties (mixture ratio 72,5:27.5)

K-vaiue 0! Paste methacrylic Detached acid Sieve analysis of methacryiic acid from Residues methyl methyl ester homopolymer per- Residue crucible Paste ester of added 1 wall and tackiness workable homo- 125 100 80 63 40 powder, kneadabie Properties 0! finished disappear at least polymer :1 u u u u g g. Alter addition atter-- paste ter tor- 1..-. 80. 1 0. i2 38 32 18 v 2. 4 Wet, dense at top 2'30 60' 2 83.3 0 16 24 36 24 2.4 do 2'30" 60' 3.... 88.3 0 2 18 60 20 3.0 ..do. 2'30 60 4 91.0 0 -4 16 46 34 2.5 .Ldo... 2'30" 60 5.... 91.8 0 14 20 20 16 1.0 Somewhat wet 2'50" 60 1 Through p.

I The noiymers contain 2.5% phthaiic acid-n-dibutyle'ster as plasticiser.

tent of acrylic acid butyl ester in the copolymer and its molecular weight. The mixture 3 has a somewhat higher content of acrylic acid butyl ester, but a very coarse particle size. The powder is excellent for strewing in, but at first very soft and tacky during spatulating; when the finished paste has become detached from the crucible wall, it is initially moist. ln this case, the grain is rather coarse in view of the lowK-value; the material therefore further characterises the existing limits. inversely, the experiment 5 shows the effect of too fine a particle size of the copolymer; the powder cannot be automaticallyadded in the desired proportion. As the molecular weight increases (mixtures 4, 6,

7, 8, 9 with K values 80.6, 82.5, 8 3.7, 87.2, 88.3) the 5 I particle size of the copolymer may become increasingly coarser. In all cases, the addition properties are satisfactory, the mass can be easily spatulated andrapidly yields a homogeneous paste which soon loses its'residual tackiness and remains workable for over one hour, Only in the mixture 9, the particles are already'rather too fine with regard to the comparatively high K-value, the powder is already difficult to strew in,tighter during spatulating, and it yields a paste which is initially rough on the outside. in the mixtures 10 and ll, even the coarser particles of the copolymerare no longer sufficient; the K-value lies beyond the acceptable range; the paste is rough at first, then dries rapidly and l is no longer usable after 40 minutes. The mixture 12 with a Kvalue of 95.3 and 34 percent of particles above 100 p. can no longer be strewn in, it is already somewhat tight for processing; the mixture 13 with the a is returned, the mixture is immediately spatulated, and

the processing propertiesare determined.

' REzEXAMPLE t TheTable shows the effect caused by a modification of the properties of the admixed homopolymer of the methacrylic acid methyl ester, taking as an example a mixture with a' copolymer of methacrylic acid methyl ester with acrylic acid butyl ester which is covered by the patent claim inrespect of the composition of the monomer, the K-value and the sieve analysis.

The mixtures l, 2, 3 and 4 contain finely divided homopolymers of methacrylic acid methyl ester with increasing molecular weights correspondingto the K- values 80.1, 83.3, 88.3 and 91.0, which are within the claimed range in respect of the K-value but must be considered too fine withregard to the sieve analysis. in all'cases, the powder mixture cannot be strewn into the monomeric methacrylic acid methyl ester in the de- K-value is far beyon'dthe limitsunder discussion. 1 sired proportion; but otherwise the paste becomes detached from the crucible wall and kneadable after the desired time, it rapidly loses its tackiness and remains workable for a sufficient period of time. Only when the homopolymer becomes appreciably coarser as in mixture 5 containing more than 50 percent of particles above 63 a, the addition properties are sufficiently improved without a deterioration of the other properties of the paste.

EXAMPLE 5 725 parts by weight ofa bead polymer of pure methacrylic acid methyl ester with a K-value of 91.8 and the sieve analysis per 125 100 80 63 40 a through 40 ,u.

14 30 2O 20 16 percent are mixed with 0.25 parts by weight benzoyl peroxide and 27.5 parts by weight of a bead-shaped copolymer of 80 parts by weight methacrylic acid methyl ester and 20 parts by weight acrylic acid ethyl ester with a K- value of 82.1 and the sieve analysis per 125 100 80 63 40 p. through 40 n which was previously sieved through a 150 p. fabric.

A weighed amount of 12 g of the mixture can be completely strewn into 4 g 4.25 cc of monomeric methacrylic acid methyl ester without leaving a residue. When spatulated, the mass remains at first moist (sugary") without cohesion; it then sets well, is kneadable after 2' 50", but initially inhomogeneous and moist, it also remains somewhat softer and more tacky than would be desirable. The residues of tackiness disappear after 5'30"; the mass is still readily workable after 1 hour.

If there are correspondingly used 12 g of a mixture of 62.5 parts by weight of the homopolymer of methacrylic acid methyl ester mentioned above, parts by weight of finely divided bead polymer of pure methacrylic acid methyl ester with a K-value of 90:8 and the sieve analysis per 80 63 40 32 y. through 32 n 0 2 12 52 34% and 27.5 parts by weight of the aforesaid copolymer with acrylic acid ethyl ester, then there remains a powder residue of 0.1 g which is returned. When spatulated, the mass is not moist (not sugary), it sets well, is kneadable after 2'20, it is not wet or inhomogeneous but immediately smooth andsupple. The residual tackiness disappears after 4'30"; the mass is still readily workable after 1 hour.

72.5 Parts by weight of the aforesaid homopolymer of methacrylic acid methyl ester with a K-value of 91.8 and the sieve analysis per 125 100 80 63 40 t through 40 ,u. t 0 14 30 20 20 16 percent are mixed with 0.25 parts by weight benzoyl peroxide and 27.5 parts by weight of the same bead-shaped copolymer of 80 parts by weight methacrylic acid methyl ester and 20 parts by weight acrylic acid ethyl ester with a K-value of 82.1, which was previously sieved through a fabric with a mesh width of 125 a, the sieve analysis now giving the following values: per 125 100 80 63 40 p, through 40 p.

2 42 36 10 8 2 percent A weighed amount of 12 g of the mixture strewn into 4 g 4.25 cc of monomeric methacrylic acid methyl ester gives a non-absorbed residue of the powder of 0.7

g which is returnedqwhen spatulated,.the mass is initially hardly moist, it is easy and soft to spatulate, kneadable after 2'30", initially still homogeneous, rough on the outside, then rather smooth; it is moderately tacky for 5'0" and still readily workable afterone hour.

If there are correspondingly used 12 g of a mixture.

of 62.5 parts by weight of the above homopolymer of methacrylic acid methyl ester, 10 parts by weight of a finely divided bead polymer of pure methacrylic acid methyl ester with a K-value of 90.8 and the sieve analysis per 63 40 32 through 32 p.

0 2 12 52 34 percent and 27.5 parts by weight of a copolymer sieved through a 125 p. fabric, then thenon-absorbedresidue of the.

powder amounts to 0.1 g; when spatulated, the mass is initially hardly moist, it then becomes appreciably tighter, though still easy, to spatulate, it is kneadable after 2'15", hardly inhomogeneous, very rapidly;

smooth and supple and also less tacky; the tackiness is no longer noticeable after 4'30", and the paste remains workable for 1 hour.

EXAMPLE 6 72.5 Parts by weight of a bead polymer of pure methacrylic acid methyl ester with a K value of 91.8 and .the

sieve analysis per 125 80 63 40p. through 40 p. 014 30 20 2016% are mixed with 27.5 parts by weight of a bead-shaped.

copolymer of 82 parts by weight methacrylic acid methyl ester and 18 parts by weight acrylic acid butyl ester with a K-value of 80.4 and the sieve analysis per 160 100 80 63 40 46 22 8 10 4 5 5 percent and with 0.25 parts by weight benzoyl peroxide. 12g of this mixture are strewn into 4 g =-4.25 cc of monomeric methacrylic acid methyl ester; there remain a residue of 0.1 g which is returned after weighing. When spatulated, the mass is initially. softand .moist, due to the comparatively low molecular weight and the excessively. coarse grain .of the copolymer. The paste is kneadable after 3'30", it is inhomogeneous and moist at first and somewhat granular, but it soon becomes smooth and homogeneous, loses the residual tackiness after 6 minutes and remains workable for over 1 hour. If the sample used consists of.12 g of a mixture of 57.5 parts by weight of the aforesaid homopolymer of methacrylic acid methyl ester, 15 parts by weight of a finely divided bead polymer of pure methacrylic acid methyl ester with a K-value of 90.8 and the sieve analysis per 80 63 40 32 a through 3211.

0 2 12 52 34 percent and 27.5 parts by weight of the said copolymer, then there also remains a very low residue of 0.05 g after strewing in; however, the mass-is wet and tacky only for a very short time, it is kneadable after 2'45", hardly! inhomogeneous and moist, it has no granular feel but is smooth and supple. it loses the residual ,tackiness after 4'45" and remains workable for over. 1 hour.

EXAMPLE 7 72.5 parts by weight of a bead polymer of pure methacrylic acid methyl ester with 'a K-value of 91.8 and the sieve analysis per 125 100 80 63 40 p. through 40 a 14 30 20 20 16 percent are mixed with 27.5 parts by weight of ahead-shaped copolymer of 80 parts by weight methacrylic acid methyl ester and 20 parts by weight acrylic acidbutyl' time, but it soon becomes smooth. it soon becomes more solid and loses the residual tackiness after 4'30 and it is still soft and kneadable after 60 minutes.

If the above mixture is replaced with a mixture consisting of 62.5 parts by weight of the aforesaid homo-' polymer of methacrylic acid methyl ester, parts by weight of a finely divided bead polymer of pure methacrylic acid methyl ester with a K-value of 90.8 and the sieve analysis per 80 63 40 32 p. through 32 p.

0 2 12 52 34 percent and with 27.5 parts by weight of the aforesaid copoly mer, then a residue of 0.4 g of, powder remains after; strewing in; the mass can be easily and evenlyspatulated and becomes tighter more rapidly. The paste is kneadable after 2'20", nicely smooth and supple, the residual tackiness disappears alreadyafter3'0", and. the paste remains excellently workable for 1 hour.

EXAMPLE 8 Seventy-five parts by weight of .a bead polymer of pure methacrylic acid methylester with a K-value of 9l.8 and the sieve analysis per 125 100 80 63 40 p. through 40 p.

0 14 30 20 16 percent are mixed with parts by weight of a bead-shaped coand with 25 parts by weight of the aforesaid copolymer, then a residue of 0.6 g of powder remains after strewing in; the mass is noticeably tighter but readily spatulated, it is kneadable'after 2'10"; in spite of the short mixing time, it is only very slightly inhomogeneous and soon becomes smooth and particularly supple. The residual tackiness disappears after 5'0", and the paste remains workable for 1 hour.

EXAMPLE 9 a are mixed with 0.25 parts by weight benzoyl peroxide and 25 parts by weight of a bead polymer which was obtained by copolymerisation of 80 parts by weight methacrylic acid methyl ester and 20 parts by weight Z-ethyl-hexylacrylic acid ester and has a K-value of 88.3 and the following sieve analysis:

per 125 100 8063 40 [1. through 40 p.

20 30 28 10 8 4 percent Twelve g of the mixtures are strewn into 4 g 4.25 cc of monomeric methacrylic acid methyl ester; 0.8 g of the powder are not absorbed by the liquid but returned after weighing. Spatulating starts at once; it is easy and smooth, and the mass soon becomes stringy. The paste is detached from the crucible wall and kneadable after 2'50". It is initially very slightly inhomogeneous, rough outside and somewhat moist, but

I soon smooth and homogeneous. The residual tackiness disappears after 5 '30", and the paste remains workable for at leastone hour.. v

If there are correspondingly used 12 g of a mixture of65 parts by weight of the aforesaid homopolymer of methacrylic acid methylester, 10 parts by weight of a polymer of 80 parts by weight methacrylic acid methyl ester and 20 parts by weight acrylic acid butyl ester with a K-value of 87.2 and the sieve analysis per 160 125 100 80 63 p. through 63 p.- 2 34 26 24 8 6 percent and with 0.25 parts by weight benzoyl peroxide.

Twelve g of the mixture are strewn into 4 g 4.25 cc of monomeric methacrylic acid methyl 'ester; 0.9 g of the powder are not absorbed but returnedatter weighing. The mass is somewhat wet at the bottom of thecrucible and the upper layer is dense. ltcan be easily spatulated; the paste is kneadable after. 2'30", somewhat inhomogeneousfor a short moment, rough outside and soft inside, but it rapidly becomes smooth. The residual tackiness disappears after 6'0, and the paste remains workable for over 1 hour.

If the above mixture is replaced with a mixture consisting of 65 parts by weight of the aforesaid homopolybead polymer of pure methacrylic acid methyl ester with a K-value of 90.8 and the sieve analysis per 80 63 40 32 p. through 32 y.

and 25 parts by weight of the aforesaid copolymer with acrylic acid 2-ethyl-hexyl1ester, then there remains a small residuei of 0.2 g of non-absorbed powder. The mass is somewhattighter when spatulated, but smooth. The pasteiskneadable already after 2'20", it is neither inhomogeneous nor moist but smooth and supple. The

residual tackiness disappears after 5'0", and the paste is again workable for at least one hour.

If the mixture ratio is 72.5 parts by weight of the firstmentioned homopolymer of methacrylic acid methyl ester to 27 .5 parts by weight of the copolymer with mer of methacrylic acid methyl ester, 10 parts by weight of a finely divided'bead polymer of pure methacrylic acid methyl ester with a K-value of 90.8 and the sieve analysis 7 per 80 63 40 .32 p. through'32 0 2 12 52 34 percent 2- ethyl-hexyl-acrylic acid ester, instead of z 25 parts by weight, then the residue after strewing in amounts to 0.5 g; the mass is somewhat tighter when spatulated,

itliskneadable after 2'30", less inhomogeneous and moist, smooth; the residual tackiness disappears after 4'l5", and the paste'remains workable for at least 1 hour.

If the mixture is prepared from 62.5 parts of the firstmentioned homopolymer of methacrylic acid methyl ester, withithe addition of 10 parts by weight of the finely divided homopolymer of methacrylic acid methyl ester and 27.5 parts of the copolymer with 2-ethylhexylacrylic acid ester, then there remains a residue after strewing in of 0.4g; the mass can immediately be In the Table, the mixture 3 corresponds to the demands made on optimum processing properties: The

residue of the powder mixture after strewing in lies below 1 g. In the mixture 4 the molecular weight is also I still in the admitted range of K-values between 76 and 95, but in the sieve analysis the proportion of copolymer particles above 80 p. amounts only to 6 percent. This means that the copolymer has too fine a grain and the mixture can no longer be automatically added in the desired proportion. A further disadvantage of the fine grain consists in that the mass is already so solid and rough during spatulating that a homogeneous-paste can not easily be obtained within the available time of 2 to 4 minutes. The mixture 2 is just within the admissible limit in respect of the addition properties, and this is also noticeable during spatulating. A coarser copolymer would have been preferable. The mixture 1 has too high a molecular weight (K value 95); consequently, the paste soon becomes elastic and does not remain workable for 1 hour.

EXAMPLE 12 Seventy-five parts by weight and 72.5 parts .by weight, respectively, of a bead polymer of pure methacrylic acid methyl ester with the K-values and sieve analyses given in the Table are mixed with 0.25 parts by weight benzoyl peroxide and with 25 and 27.5 parts by weight, respectively, of a bead polymer which was obtained by copolymerisation of 60 parts by weight methacrylic acid methyl ester and 40 parts by weight methacrylic acid butyl ester and has a K-value of 86.7 and the following sieve analysis per 125 I 80 63 40 a through 40 p.

12 i0 22 20 20 16 percent Each time, l2 g of the mixture are strewn into 4g 4.25 cc of monomeric methacrylic acid-methyl ester,

the weight of the non-absorbed powder is determined, This is returned, and the processing properties are determined.

The Table shows the effect caused by a modification of the properties of the admixed homopolymer of methacrylic acid methyl ester, taking as an example the mixture with a copolymer of methacrylic acid methyl ester with methacrylic acid butyl ester which is in accordance'with the present invention in respect of composition of the monomer, the K-value and the sieve analysis. v I The mixture 1 contains a very coarse homopolymer of methacrylic acid methyl ester witha substantial proportion ,of particles above 125 p. and a comparatively low K-value below the claimed range.- The powder'is easily strewn in. The mixture also becomes kneadable within a fairly short time, but the pasteis inhomogeneous, it remains moist and softand is tacky for appreciably longer than 6 minutes. In mixture 2 there is used a homopolymer of methacrylic acid methyl ester which is too finely divided, it contains 72 percent of particles below 63 u. The powder mixtures cannot be addedin the desired proportion, a substantial residue remains, and the time available for processing falls to below one hour in spite of the comparatively low K-value. The mixture 3 is prepared with homopolymer of methacrylic acid methyl ester the particles of which is too coarse. The paste tends initially to become inhomogeneous and then remains slightly granular. The mixtures 4, 5 and 6 with homopolymersof the K-values9l.5, 91,8 and l02.7 are within the claimed range in respect of the molecular weights as well as of the sieve analy- Processing properties at mixture ratio 75:25 a Paste 8 Inhomogeneous. moist.

2 Smooth-.......

8 15 Initially briefly inhomogeneous, then smooth, sllghtlly granu or. 2 30 Smooth.......

60 0.4 Some- Bolt, soon what stringy.

- wet.

1.8 Wet, Tight, dense viscous. at top.

1.0 Wet...-

60 0.9 Somewhat Somewhat wet. tigpter,

strn

60 0.3 Hardly Somew liet wet. stringy,

good.

60 0.7 Notwet... Good, not

moist,

tight.

50 2.1 Wet, Rough dense at top. viscous.

2 45 Inhomogeneous, moist, soIt. 2 20 Smooth 2 25 Smooth,s1ightly granular.

2 25 Briefly moist, then smooth. 2 46 Initially very slightly inhomogeneous then smooth. 2 15 Smooth.

28 l 12 18 0.0 Notwet--- Soit, soon stringy. 46 26 1.7 Wet. Tight, dense viscous. at top. 4 0.6 Notwet... Brieliywet, sets lmmediateiy.

30 20 10 0.3 Hardly Good; wet. rather soit.

28 20 22 20 0.7 Some- Immediwlmt ately wet. stringy,

somewhat tight.

39 23 16 12 2.2 Wet, Rough and dense viscous. at top.

1 Through 4011..

ses. The powder can automatically be strewn into the liquid in the desired proportion; the paste is readily spatulated so that it becomes soon detached from the crucible wall and'kneadable; the paste is smooth, loses its residual tackiness sufficiently 'fast, and remains workable for at least one hour. In contrast thereto, the

last mixture 7 contains a homopolymer of methacrylic acid methyl ester which is above the claimed limit in respect of the K-value; the powder can no longer be strewn in without a substantial residue, although the sieve analysis is stillwithin the chosen range. The mass is rough during spatulating, and the paste remains workable for less than one hour.

EXAMPLE l3 Seventy-five parts by weight and 25 parts by weight, respectively, of a bead polymer of pure methacrylic acid methyl ester with a K-value of9 l .8 and the following sieve analysis: per 125 I 80 63 40 a through 40 are mixed with 0.25 parts by weight benzoyl peroxide and with and 27.5 parts by weight, respectively, of a bead polymer obtained by copolymerisation of'methacrylic acid methyl ester with methacrylic acid-n-decyl ester. Each time, 12 g of the mixture are strewn into 4 .g 4.25 cc of monomeric methacrylic acid methyl ester, the weight of the non-absorbed powder is determined, this is returned, the mass is spatulated and the processing properties are determined.

It can be seen from the Table how the content of methacrylic acid-n-decyl ester in the copolymer, the viscosimetric molecular weight, given in form of the i(- value, and the particle size affect the processing properties of the mixture of the two components with monomeric methacrylic acid methyl ester:

If the contentof methacrylic acid-n-decyl ester in the copolymer ([5 percent) and the K-value are too low (mixtures l and 2), then the powder can be added almost in the desired proportion of 3 parts by weight of powder to 1 part by weight of liquid, but the mass sets only slowly, it remains moist sugary for a long time; when it is spatulated, it becomes detached from the crucible wall only after 5 minutes; when kneaded, it is inhomogeneous, moist slushy, and completely loses its tackiness only after a prolonged period of time. It is even possible to create conditions (series 2) where powder can be added in a higher proportion than 3 1 so that the surface of the paste which is initially moist becomes again dry and the mass sets better, but the processing range falls to below minutes.

The content of n-decyl-methacrylate in the copolymer must be increased to the vicinity of 20 parts by weight (experiment 3 and the following), and the K- value must be brought to at least 76, perferably 80, in order to comply with the condition that less than 1 g of residue remains when l2 g of powder are strewn into 4 g of monomeric methacrylic acid methyl ester; that the massbecomes kneadable after 4 minutes, that it loses its-residual tackiness after about 6 to 6% minutes, and that it remains workable for at least 60 minutes. Numbers 3 and 6 meet these demands, since also the sieve analysis is within the correct range. At a low K- value of below 80, a material in which 14 percent of particles are above80 p. (experiment 3, K-value 76.3; see also experiment 4, K-value 78.2) is just about usable. In this case, the comparatively fine grain permits of a tolerable processing, although the mass sets relatively slowly, due to the low molecular weight, becomes kneadable relatively late, and remainsmoist and tacky, for a long time. However, if the K-values are above 80, the sieve analysis must showat least 25 percent of particles above n if all demands are to be met (experimens 5 and 6). When a powder with a coarser copoly mer is strewn in, the mass-is initially moist sugary for a short time, but it swells rapidly. to become workable and it remains usable for at least 1 hour. When the molecular weight is further increased beyond K-values of (mixtures 7 to 10), then the time for processing falls below one hour. Even if the grain is very coarse (experiment 9), the paste rapidly acquires a dry, loose and more or less elastic character, and finally .at an extremely high molecular weight, the mass cannot be combined at all to form a useful part (experiment 10).

When the contentof methacrylic acid-n-decyl ester in'the copolymer is increased to 22.5 to 25 percent (Nos. 11 to 18), then the stated copolymers with, the claimed ll-values give mixtures having all the processing properties required, provided the sieve analysis shows a sufficient proportion of particles above 80 p. in the copolymer. With a K-value above 90, even a very coarse grain of the copolymer (experiment 16) can no longer improve matters.

An increase of the mixture ratio of copolymer to homopolymer from 25 75 to 27.5 72.5 has throughout the effect that the residue after addition is somewhat higher, in most cases without becoming detrimental; that-the mass sets somewhat more rapidly when spatulated, that the paste is somewhat less moist when kneaded and that it loses its residual tackiness somewhat sooner especially if the K-value is low; but; on the other hand, the paste becomes sooner dry and strongly rubber-like when the K-value is high. A modification of the mixture ratio between-homopolymer. and copolymer the essential properties of which are determined by the claim, thus offers a certain limited scope for improvement. If the molecular weight is low and the grain too coarse, and the mass therefore sets too slowly, more copolymer will be added; inversely, less will be added, when the mass is too tightduring spatulating because the molecular weight is too high or the grain is too fine.

EXAMPLE 14': Seventy-five and 725 parts by weight, respectively,

of a bead polymer of pure -.methacrylic acid methyl ester with the K-values and sieve analyses given in the Table are mixed with 0.25 parts by weight-benzoyl peroxide'and with 25 and 27.5 parts by weight, respectively, of a bead polymer which v'was obtained by copolymerisation of 75 parts by weight methacrylic of the properties of theadmixed homopolymer of methacrylic acid methyl ester, taking asan example the mixture with ,a copolymer of methacrylic acid methyl ester with methacrylic acid-n-decyl ester which isin accordance with the present inventionzin respect of the composition of the monomer, the K value and the sieve analysis. 

2. a mixture of said finely divided polymer of methacrylic acid methyl ester and a polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a particle size one-fifth to one-half as large as said finely divided polymer of methacrylic acid methyl ester; or
 2. a copolymer of 18-30 percent of one or more methacrylic acid esters containing seven to 14 carbon atoms in the alcohol residue, the balance comprising methacrylic acid methyl ester and 0 to 5 percent of a further comonomer, and having a K-value of 76-80 when the copolymer has a sieve analysis of at least 10 percent of particles above 80 Mu , and a K-value of 80-90 when the copolymer has a sieve analysis of at least 25 percent of particles above 80 Mu ; or
 2. The composition of claim 1, wherein component A is a finely divided polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a sieve analysis of at least 98 percent of particles below 125 Mu and more than 50 percent of particles above 63 Mu .
 3. a copolymer of 20-50 percent of one or more methacrylic acid esters containing four to six carbon atoms in the alcohol residue, the balance comprising methacrylic acid methyl ester and 0 to 5 percent of a further comonomer, and having a K-value of 76-95 and a sieve analysis of at least 15 percent of particles above 80 Mu .
 3. a mixture of a. a coarser polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a sieve analysis of at least 99 percent of particles below 150 Mu and more than 50 percent of particles above 63 Mu , and b. a polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a particle size one-fifth to one-half as large as said coarser polymer of methacrylic acid methyl ester; and component B being:
 3. The composition of claim 1, wherein component A is a mixture of a finely divided polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a sieve analysis of at least 98% of particles below 125 Mu and more than 50 percent of particles above 63 Mu and a polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a particle size one-fifth to one-half as large as said finely divided polymer of methacrylic acid methyl ester.
 4. The composition of claim 1, wherein component A is a mixture of a coarser polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a sieve analysis of at least 99 percent of particles below 150 Mu and more than 50 percent of particles above 63 Mu , and a polymer of methacrylic acid methyl ester containing 0 to 2 percent of a comonomer and having a K-value of 75-120 and a particle size one-fifth to one-half as large as said coarser polymer of methacrylic acid methyl ester.
 5. The composition of claim 1, wherein component B is a copolymer of 15-30 percent of one or more acrylic acid esters, the balance being methacrylic acid methyl ester and 0 to 5 percent of a further comonomer, and having a K-value of 76-95 and a sieve analysis of at least 15 percent of particles above 100 Mu .
 6. The composition of claim 1, wherein component B is a copolymer of 18-30 percent of one or more methacrylic acid esters containing seven to 14 carbon atoms in the alcohol residue, the balance comprising methacrylic acid methyl ester and 0 to 5 percent of a further comonomer, and having a K-value of 76-80 and a sieve analysis of at least 10 percent of particles above 80 Mu , or a K-value of 80-90 and a sieve analysis of at least 25 percent of particles above 80 Mu .
 7. The composition of claim 1, wherein component B is a copolymer of 20-50 percent of one or more methacrylic acid esters containing four to six carbon atoms in the alcohol residue, the balance comprising methacrylic acid methyl ester and 0 to 5 percent of a further comonomer, and having a K-value of 76-95 and a sieve analysis of at least 15 percent of particles above 80 Mu .
 8. The composition of claim 1, wherein there is 80 to 70 parts of component A per 20-30 parts of component B.
 9. The composition of claim 1, wherein the polymers and copolymers are bead-shaped.
 10. The composition of claim 2, wherein the K-value of the finely divided polymer is from 80 to
 100. 11. The composition of claim 3, wherein said finely divided polymer constitutes 50-95 percent of said mixture.
 12. The composition of claim 4, wherein said finely divided polymer constitutes 50-95 percent of said mixture.
 13. The composition of claim 5, wherein the copolymer contains 20-25 percent of said acrylic acid esters.
 14. The composition of claim 5, wherein the alcohol residues of said acrylic acid esters contain from one to eight carbon atoms.
 15. The composition of claim 5, wherein said acrylic acid ester is methyl, ethyl, butyl or 2-ethylhexyl acrylate.
 16. The composition of claim 5, wherein the copolymer has not more than 80 percent of the particles above 100 Mu .
 17. The composition of claim 6, wherein the copolymer contains 20-25 percent of said methacrylic acid esters containing seven to 14 carbon atoms in the alcohol residue.
 18. The composition of claim 6, wherein the copolymer of K-value between 76 and 80 has at least 25 percent particles above 80 Mu .
 19. The composition of claim 6, wherein the methacrylic acid ester containing seven to 14 carbon atoms in the alcohol residue is methacrylic acid n-decyl ester.
 20. The composition of claim 7, wherein the copolymer contains 35-40 percent of said methacrylic acid esters containing four to six carbon atoms in the alcohol residue.
 21. The composition of claim 7, wherein the copolymer has at least 25 percent of particles above 80 Mu .
 22. The composition of claim 7, wherein the methacrylic acid ester containing four to six carbon atoms in the alcohol residue is butyl methacrylate.
 23. The composition of claim 1, wherein component A is coarser than component B. 